bismuth oxychloride

Bismuth

Bismuth is a chemical element that has the symbol Bi and atomic number 83. This heavy, brittle, white crystalline trivalent poor metal has a pink tinge and chemically resembles arsenic and antimony. Of all the metals, it is the most naturally diamagnetic, and only mercury has a lower thermal conductivity. It is generally considered to be the last naturally occurring stable, non-radioactive element on the periodic table, although it is actually slightly radioactive, with an extremely long half-life.

Bismuth compounds are used in cosmetics, medicines, and in medical procedures. As the toxicity of lead has become more apparent in recent years, alloy uses for bismuth metal as a replacement for lead have become an increasing part of bismuth's commercial importance.

Elemental bismuth is one of very few substances of which the liquid phase is denser than its solid phase (water being the best-known example). Because bismuth expands on freezing, it was long an important component of low-melting typesettingalloys, which needed to expand to fill printing molds.

Isotopes

While bismuth was traditionally regarded as the element with the heaviest stable isotope, bismuth-209, it had long been suspected to be unstable on theoretical grounds. This was finally demonstrated in 2003 when researchers at the Institut d'Astrophysique Spatiale in Orsay, France, measured the alpha emissionhalf-life of 209Bi to be 1.9 x 1019 years, over a billion times longer than the current estimated age of the universe. Owing to its extraordinarily long half-life, for nearly all applications bismuth can be treated as if it is stable and non-radioactive. The radioactivity is of academic interest, however, because bismuth is one of few elements whose radioactivity was suspected, and indeed theoretically predicted, before being detected in the laboratory.

"Artificial bismuth" was commonly used in place of the actual metal. It was made by hammering tin into thin plates, and cementing them by a mixture of white tartar, saltpeter, and arsenic, stratified in a crucible over an open fire.

Bismuth was also known to the Incas and used (along with the usual copper and tin) in a special bronzealloy for knives.

Occurrence and production

In the Earth's crust, bismuth is about twice as abundant as gold. It is not usually economical to mine it as a primary product. Rather, it is usually produced as a byproduct of the processing of other metal ores, especially lead, copper, tin, silver, and gold, but also tungsten or other metal alloys.

According to the USGS, world 2006 bismuth mine production was 5,700 tonnes, of which China produced 3,000 tonnes, Mexico 1,180 tonnes, Peru 950 tonnes, and the balance Canada, Kazakhstan and other nations. World 2006 bismuth refinery production was 12,000 tonnes, of which China produced 8,500 tonnes, Mexico 1,180 tonnes, Belgium 800 tonnes, Peru 600 tonnes, Japan 510 tonnes, and the balance Canada and other nations.

The difference between world bismuth mine production and refinery production reflects bismuth's status as a byproduct metal. Bismuth travels in crude lead bullion (which can contain up to 10% bismuth) through several stages of refining, until it is removed by the Kroll-Betterton process or the Betts process. The Kroll-Betterton process uses a pyrometallurgical separation from molten lead of calcium-magnesium-bismuth drosses containing associated metals (silver, gold, zinc, some lead, copper, tellurium, and arsenic), which are removed by various fluxes and treatments to give high-purity bismuth metal (over 99% Bi). The Betts process takes cast anodes of lead bullion and electrolyzes them in a lead fluosilicate-hydrofluosilicic acid electrolyte to yield a pure lead cathode and an anode slime containing bismuth. Bismuth will behave similarly with another of its major metals, copper. Thus world bismuth production from refineries is a more complete and reliable statistic.

According to the Bismuth Advocate News, the price for bismuth metal from year-end 2000 to September 2005 was stuck in a range from $2.60 to $4.15 per lb., but after this period the price started rising rapidly as global bismuth demand as a lead replacement and other uses grew rapidly. New mines in Canada and Vietnam may relieve the shortages, but prices are likely to remain above their previous level for the foreseeable future.

Crystals

Though virtually unseen in nature, high-purity bismuth can form distinctive hopper crystals. These colorful laboratory creations are typically sold to collectors. Bismuth is relatively nontoxic and has a low melting point just above 271 °C, so crystals may be grown using a household stove, although the resulting crystals will tend to be lower quality than lab-grown crystals.

In 1997 an antibody conjugate with Bi-213, which has a 45 minute half-life, and decays with the emission of an alpha-particle, was used to treat patients with leukemia.

In 2001, Professor Barry Allen and Dr. Graeme Melville at St. George Hospital in Sydney successfully produced Bi-213 in linac experiments which involved bombarding radium with bremsstrahlung photons. This cancer research team used Bi-213 in its Targeted Alpha Therapy (TAT) program.

The delta form of bismuth oxide when it exists at room temperature is a solid electrolyte for oxygen. This form normally only exists above and breaks down below a high temperature threshold, but can be electrodeposited well below this temperature in a highly alkaline solution.

In the early 1990s, research began to evaluate bismuth as a nontoxic replacement for lead in various applications:

As noted above, bismuth has been used in solders; its low toxicity will be especially important for solders to be used in food processing equipment and copper water pipes.

Replacement for lead in shot and bullets. The UK, U.S., and many other countries now prohibit the use of lead shot for the hunting of wetland birds, as many birds are prone to lead poisoning due to mistaken ingestion of lead (instead of small stones and grit) to aid digestion. Bismuth-tin alloy shot is one alternative that provides similar ballistic performance to lead. (Another less expensive but also more poorly performing alternative is "steel" shot, which is actually soft iron.)

Bismuth core bullets are also starting to appear for use in indoor shooting ranges, where fine particles of lead from bullets impacting the backstop can be a chronic toxic inhalant problem. Owing to bismuth's crystalline nature, the bismuth bullets shatter into a non-toxic powder on impact, making recovery and recycling easy. The lack of malleability does, however, make bismuth unsuitable for use in expanding hunting bullets.

According to the USGS, U.S. bismuth consumption in 2006 totaled 2,050 tonnes, of which chemicals (including pharmaceuticals, pigments, and cosmetics) were 510 tonnes, bismuth alloys 591 tonnes, metallurgical additives 923 tonnes, and the balance other uses.

Compounds

Precautions

Bismuth is not known to be toxic, compared to its periodic table neighbours (lead, antimony, and polonium), although some compounds (including bismuth chloride due to its corrosive acidity) are toxic and should be handled with care. As with lead, overexposure to bismuth can result in the formation of a black deposit on the gingiva, known as a bismuth line.